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( 12 ) United States Patent US009770709B2 (12 ) United States Patent ( 10 ) Patent No. : US 9 ,770 , 709 B2 Swager et al. (45 ) Date of Patent: * Sep . 26 , 2017 ( 54 ) COMPOSITIONS COMPRISING C07C 235 /40 ( 2013. 01 ) ; CO7D 303 / 38 FUNCTIONALIZED CARBON - BASED ( 2013. 01 ) ; CO7D 493/ 22 (2013 . 01 ) ; CO7F 1/ 08 NANOSTRUCTURES AND RELATED ( 2013 .01 ) ; C07F 5 / 00 ( 2013 .01 ) ; C07F 5 / 06 METHODS ( 2013. 01 ) ; C07F 7 / 28 ( 2013 .01 ) ; C07F 15 /006 (2013 .01 ) ; CO7F 15 /02 ( 2013. 01 ) ; HONG (71 ) Applicant: Massachusetts Institute of 11 /36 ( 2013. 01 ) ; HOTM 4 /625 ( 2013 .01 ) ; YO2E Technology , Cambridge, MA (US ) 60 / 13 ( 2013 .01 ) (58 ) Field of Classification Search (72 ) Inventors : Timothy M . Swager, Newton , MA CPC . .. .. CO1B 31 /0213 ; C01B 31 /0484 ; C01B (US ) ; William R . Collins, Durango , 31/ 0273 ; B82Y 40 / 00 ; B82Y 30 / 00 ; CO (US ) ; Wiktor Lewandowski, A24D 3 / 163 ; C07D 493 / 22 ; C07D Warsaw (PL ) ; Ezequiel Schmois , 303 /38 ; H016 11 / 36 ; CO7F 5 /06 ; CO7F Cambridge , MA (US ); Stefanie Sydlik , 5 / 00 ; C07F 7 /28 ; CO7F 1 / 08 ; C07F Cambridge, MA (US ) ; Joseph Walish , 15 / 006 ; CO7F 15/ 02 ; B01J 31 / 12 ; C07C Cambridge , MA ( US ) ; John B . Goods , 235 / 40 ; HOTM 4 /625 ; YO2E 60 / 13 Cambridge, MA (US ) USPC .. 534 / 15 ; 549 /543 ; 556 / 112 , 136 , 140 , ( 73 ) Assignee : Massachusetts Institute of 556 / 170 , 52 ; 562 /507 Technology , Cambridge , MA (US ) See application file for complete search history. ( * ) Notice : Subject to any disclaimer , the term of this (56 ) References Cited patent is extended or adjusted under 35 U .S . C . 154 (b ) by 5 days. U . S . PATENT DOCUMENTS 3 ,450 , 878 A 6 / 1969 Pezdirtz et al. This patent is subject to a terminal dis 3 , 915 ,706 A 10 / 1975 Limburg et al. claimer. 4 ,616 ,237 A 10 / 1986 Pettigrew et al . 5 , 753 ,088 A 5 / 1998 Olk (21 ) Appl. No. : 14 /670 , 232 6 ,616 , 497 B1 9 / 2003 Choi et al. 6 , 652 , 958 B2 11/ 2003 Tobita 6 , 705 , 910 B2 3 /2004 Sheu et al. ( 22 ) Filed : Mar . 26 , 2015 6 , 902 , 658 B2 6 / 2005 Talin et al. 6 , 958 , 216 B2 10 / 2005 Kelley et al . (65 ) Prior Publication Data 7 , 014 , 743 B2 3 / 2006 Zhou et al. 7 , 187 , 115 B2 3 /2007 Seon US 2015/ 0336092 A1 Nov . 26 , 2015 7 ,303 , 875 B1 . 12 /2007 Bock et al. 7 ,365 , 100 B2 4 / 2008 Kuper et al. Related U . S . Application Data 7 , 556, 775 B2 7 / 2009 McGill et al . 7 , 854 ,826 B2 12 / 2010 So et al. (63 ) Continuation of application No . 13 / 288 , 769, filed on 7 , 871 , 533 B11 / 2011 Haiping et al. Nov . 3 , 2011 , now abandoned . 8 ,187 , 887 B2 5 /2012 Swager et al. ( 60 ) Provisional application No . 61/ 409, 844 , filed on Nov . ( Continued ) 3 , 2010 . FOREIGN PATENT DOCUMENTS (51 ) Int . CI. 1995143 A 7 / 2007 CO7F 7 / 28 ( 2006 .01 ) 63 - 221278 A 9 / 1988 CO7F 15 / 00 ( 2006 .01 ) 2007 - 524735 A 8 /2007 CO7F 15 /02 ( 2006 . 01 ) 2008 -047855 A 2 / 2008 CO7F 5 / 06 ( 2006 . 01 ) ZEEEE 2008 -520414 A 6 /2008 CO7F 1 /08 ( 2006 .01 ) ( Continued ) B01J 31/ 12 ( 2006 .01 ) C07C 235 / 40 ( 2006 .01 ) OTHER PUBLICATIONS CO7D 303 /38 ( 2006 .01 ) CO7F 5 / 00 ( 2006 . 01 ) Shu et al ., Electrochemical Intercalation of Lithium into Graphite . COIB 31 /02 ( 2006 .01 ) J . Electrochem . Soc . Apr. 1993 ; 140 ( 4 ) : 922 - 927 . COIB 31 /04 ( 2006 . 01 ) (Continued ) C07D 493 /22 ( 2006 . 01 ) A24D 3 / 16 ( 2006 . 01 ) Primary Examiner — Daniel C McCracken HOIG 11/ 36 ( 2013 . 01 ) (74 ) Attorney , Agent, or Firm — Wolf , Greenfield & B82Y 30 /00 ( 2011 .01 ) Sacks, P . C . B82Y 40 / 00 ( 2011 . 01 ) HOIM 4 /62 ( 2006 .01 ) (57 ) ABSTRACT ( 52 ) U . S . CI. The present invention generally relates to compositions CPC . .. .. .. .. B01J 31/ 12 (2013 .01 ) ; A24D 3 / 163 comprising and methods for forming functionalized carbon (2013 .01 ) ; B82Y 30 /00 ( 2013 .01 ) ; B82Y 40/ 00 based nanostructures . (2013 .01 ) ; COIB 31/ 0213 ( 2013 .01 ) ; COIB 31/ 0273 ( 2013 . 01 ) ; COIB 31/ 0484 ( 2013 .01 ) ; 18 Claims, 31 Drawing Sheets US 9 , 770 , 709 B2 Page 2 (56 ) References Cited Invitation to Pay Additional Fees for PCT/ US2009 /001396 mailed Dec . 10 , 2009 . U . S . PATENT DOCUMENTS International Search Report and Written Opinion for PCT/ US2009 / 001396 mailed Apr. 22, 2010 . 8 , 212 , 132 B27 / 2012 Swager et al . 8 ,426 , 208 B24 / 2013 Swager et al. International Preliminary Report on Patentability for PCT/ US2009 / 8 ,456 ,073 B2 6 /2013 Swager et al. 001396 mailed Sep . 16 , 2010 . 8 ,476 ,510 B2 * 7 / 2013 Swager . C01B 31/ 0213 International Search Report and Written Opinion for PCT/ US2009 / 257 / 40 006512 mailed Oct . 22 , 2010 . 8 , 735, 313 B2 5 /2014 Swager et al. International Preliminary Report on Patentability for PCT /US2009 / 8 , 951 , 473 B2 2 / 2015 Wang et al. 006512 mailed Jun . 23 , 2011 . 9 , 114 ,377 B2 8 / 2015 Swager et al. Invitation to Pay Additional Fees for PCT/ US2010 /051610 mailed 9 , 267 ,908 B2 2 / 2016 Wang et al. Dec . 27 , 2011 . 2002/ 0037457 Al 3 / 2002 Choi 2002/ 0171079 Al 11 / 2002 Braun et al . International Search Report and Written Opinion for PCT/ US2010 / 2004 / 0067530 A1 4 / 2004 Gruner 051610 mailed Mar. 5 , 2012 . 2004 /0161360 A1 8 /2004 Ogawa et al . International Preliminary Report on Patentability for PCT/ US2010 / 2005 /0067406 A1 3 /2005 Rajarajan et al . 051610 mailed Apr. 19 , 2012 . 2005 / 0070658 Al 3 /2005 Ghosh et al. Invitation to Pay Additional Fees for PCT/ US2010 /055395 mailed 2006 /0045838 A1 3 / 2006 Lucien Malenfant et al. Dec . 7 , 2011. 2006 / 0057927 Al 3 / 2006 Kang et al. 2006 / 0063464 Al 3 / 2006 Kang et al. International Search Report and Written Opinion for PCT/ US2010 / 2006 /0142148 Al 6 / 2006 Ma et al. 055395 mailed Mar. 20 , 2012 . 2006 / 0151382 A1 7 / 2006 Petrik International Preliminary Report on Patentability for PCT/ US2010 / 2006 / 0174385 Al 8 / 2006 Gruber et al . 055395 mailed May 18 , 2012 . 2006 /0202168 A1 9 / 2006 Barrera et al. International Search Report and Written Opinion for PCT/ US2011 / 2007/ 0178477 A1 8 / 2007 Joiner et al . 059155 mailed Jun . 25 , 2013 . 2007 / 0179272 Al 8 / 2007 Tobe et al. International Preliminary Report on Patentability for PCT /US2011 / 2007/ 0295347 Al 12 / 2007 Paine et al. 059155 mailed Jul. 11 , 2013 . 2008 /0076816 Al 3 / 2008 Bianco et al . International Search Report and Written Opinion for PCT/ US2011 / 2008 /0131658 A1 6 / 2008 Wakharkar et al. 059168 mailed Jun . 19 , 2013 . 2008 /0221240 AL 9 / 2008 Swager et al . International Preliminary Report on Patentability for PCT/ US2011 / 2008/ 0302998 AL 12 / 2008 Hong et al. 2009/ 0058258 AL 3 / 2009 Chang et al. 059168 mailed Jul. 18 , 2013 . 2009 / 0305089 Al 12 / 2009 Minteer et al . International Search Report and Written Opinion for Application 2009/ 0306427 Al 12 / 2009 Martinez - Rubi No . PCT/US2013 /029621 mailed May 8 , 2013. 2010 /0028559 Al 2 / 2010 Yan et al. International Preliminary Report on Patentability for PCT/ US2013 / 2010 /0179054 Al 7 / 2010 Swager et al. 029621 mailed Apr. 30 , 2015 . 2010 / 0222432 A1 9 / 2010 Hua [No Author Listed ] TGP _ H Carbon Fiber Paper . Toray Automotive 2011/ 0089051 A1 4 /2011 Wang et al. Solutions. Toray Industries (America ), Inc . Available at http : / /www . 2011 /0136007 Al 6 / 2011 Zhamu et al . toray - auto .us / poductrs / carbon _ papers _ fuel _ cells . html. Last 2011/ 0171629 A1 7 / 2011 Swager et al. accessed Nov . 19 , 2010 . 2 pages . 2012 /0116094 A1 5 / 2012 Swager et al. [No Author ] Definition of “ ketone, ” accessed online at http : / / 2012 /0171093 Al 7 / 2012 Swager et al. dictionary .reference . com /browse /ketone ? s = t on Jun . 14 , 2014 . 2013 /0113359 Al 5 / 2013 Swager et al. [No Author ] Definition of “ moiety , ” accessed online at http : // 2014 /0107326 A1 4 / 2014 Swager et al. dictionary . reference. com /browse /moiety on Dec . 21, 2014 . Albert et al ., Cross - reactive chemical sensor arrays . Chem Rev. Jul. FOREIGN PATENT DOCUMENTS 12 , 2000 ; 100 ( 7 ) :2595 -626 . 2009 -022919 A 2 / 2009 Bai et al. , Gas Sensors Based on Conducting Polymers . Sensors. JP 2009 - 268961 A 11 / 2009 2007 ; 7 : 267 - 307 . JP 2010 - 129385 A 6 / 2010 Baughman et al ., Carbon Nanotubes — The Route Toward Applica WO WO 01/ 10779 A1 2 / 2001 tions. Science . 2002; 297 ( 2 ) :787 -92 . WO WO 2004 / 113275 A2 12 / 2004 Becker et al. , The Influence of Surface Strain on the Chemical wo WO 2006 /055670 A2 5 / 2006 Reactivity of Fullerene Ions: Addition Reactions with WO WO 2006 / 104046 A1 10 / 2006 Cyclopentadiene and 1 , 3 -cycolhexadiene . International Journal of WO WO 2006 / 115486 Al 11 / 2006 Mass Spectrometry and Ion Processes. 1997 ; 167 / 168 :519 - 24 . WO WO 2007 /033189 A1 3 / 2007 Bekyarova et al . , Chemical modification of epitaxial graphene : W0 WO 2007 / 098578 A1 9 / 2007 spontaneous grafting of aryl groups . J Am Chem Soc . Feb . 4 , WO WO 2007 / 143028 A2 12 / 2007 2009 ; 131 ( 4 ) : 1336 - 7 . WO WO 2008 / 133779 A2 11 / 2008 WO WO 2009 /085015 A1 7 / 2009 Chen et al. , Dissolution of Full- Length Single -Walled Carbon WO WO 2009 / 136978 A2 11 / 2009 Nanotubes . J Phys Chem B . 2001 ; 105 :2525 - 28 . WO WO 2010 /022164 Al 2 /2010 Chen et al. , Noncovalent functionalization of carbon nanotubes for WO WO 2012 /061607 A2 5 / 2012 highly specific electronic biosensors . Proc Natl Acad Sci USA . Apr. 29 , 2003 ; 100 ( 9 ) :4984 - 9 .
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